Paul Dennis edited untitled.tex  over 8 years ago

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Substitution of $R_{47}$ (equation 2) and $R_{47}^{*}$ (equation 5) into equation 1 allows determination of $\Delta_{47}$. Evaluation of $\Delta_{48}$ and $\Delta_{49}$ follows the same steps as above. The complete data reduction algorithm and it’s implementation in a Mathematica program for data obtained on the MIRA mass spectrometer is included in the supplementary information.  Finally, using themethod outlined by Dennis et al. (2011) and the  heated and water equilibrated gas standards we determine a transfer function betweenmeasurements made on  the local scale scale, that is for measurements made  with reference respect  to the mass spectrometer working reference gas gas, and  the absolute reference frame (ARF). (ARF) \citep{Dennis:2011jd}.  All the results are reported with respect to the ARF. The full data set including results reported on both the local and ARF scales are included with the supplementary information. (iii) Temperature subsection{Temperature  estimation using Δ47 $\Delta_{47}$}  Using the clumped isotope composition of carbonate minerals as a geothermometer is a relatively immature technique. Of particular importance is the lack of agreement on the calibration between the deviation from a stochastic distribution of the isotopes and temperature. There exists a large number of calibrations with varying degrees of sensitivity. Moreover, most of these calibrations have been made over a restricted range of temperatures based on the collection of biogenic carbonates from environments with known temperature (e.g. references). More recently calibrations have become available for inorganically precipitated calcites. However these have not served to resolve the origin of the differences.  What is clear from these studies is that differences between calibrations are laboratory dependent. i.e. measurements of unknown samples when converted to a temperature only make geological sense when the local Δ47 - T calibration is used. If another laboratories calibration is used then unrealistic temperatures are often estimated. This points to significant methodological issues associated with sample preparation and mass spectrometry that have yet to be resolved. We don’t discuss these here. For this study we have used the UEA determined calibration to translate Δ47 values for carbonates into temperature.    (6)